Process of revivifying spent clarifying and decolorizing agents



.June 4, 1929. M. L. cHAPPELL.

PRQCESS OF REVIVIFYING SPENT GLARIFYING AND, DEGOLORIZIING AGENTS Filed March 424, 1926 IWENTOR.

BIA NN gm A TTORNEYS Patented .lume 4, .1929` "smear russa ENCE..

MARVIN L. CHAPPELL, F LOS ANGELES, CALIFORNIA, ASSIGNOR, BY MESNE ASSIGN- MENTS, TO CONTACT FILTRATION COMPANY, OF SAN FRANCISCO, CALIFORNIA, A

f CORPORATION OF DELAVJARE.

PROCESS OF REVIVIFYING SPENT CLARIFYING AND DECOLORIZING AGENTS.

Application led March 24, 1926. Seria1 No. 97,067. i

Y This invention relates to the revivification of spent clarifying and decolorizing agents which have been used for the clarifying and decolorizing of petroleum oils, and is particu- 5 larly directed to those classes of decolorizing and clarifying agents which, as their basic' ingredient, .include hydrous aluminumsilicate in aratio of less than 1 part of alumina (A120.) to

example, as the artificially produced clarifying and decolorizing agents derived from the acidtreatment of a Montmorillonitetype of clay, in accordance with the processof the copending application of Marvin L. Chappell, Richard F. Davis, and Merle M. Moore,

filed August 1, 1921, Serial No. 488,952.

An object of the present invention is to provide a method which is adapted not only to completely revivify spent clarifying and decolorizing agents of the above type, but also to obtain an added decolorizing efficiency of from 1 to as high as 15 per cent higher, there-v by forming an agent having a clarifying and decolorizing efficiency rangeY from 1,01 to as vhigh as 115 per cent as compared with the agent before use.

More specifically, f have discovered that clarifying and decolorizing agents which comprise as their basic ingredient hydrous 3o aluminum silicate can be most effectively revivi fied by the use of a color solvent containing sulfuric acid provided that the quantityv of sulfuric acid employed upon the agent is Within certain limits hereinafter setforth.v

The clarifying and decolorizing agents to be treated by this process belong to the class of h vdrous aluminum silicate which, beforeacidtreatment, have substantially no natural l clarifying and decolorizing properties,'that 40 is, which could not be commercially profitably employed for such purposes. Such clays before being converted into a'clarifying and decolorizing agent by an acid treatment. are silicates of aluminum of the Montmorillonite type and of the approximate formula H2Al2Si,O12N(H2 O').

As a.specific example,'the following isan 4 parts of silica (Si02) such, forv analysis of a typical Montmorillonite clay before and after being converted into a decolorizing agent by a clarifying' treatment:

@Zay from Omg, San Diego Codatg/,OaZi/or- 4 ma... Air dried).

y Percent. Water at 105o C., H2C 13.55 Water over 105o C., H2O 5.77 f Silica, SiO2 54.56 Alumina, A1,()3 18.61 4Iron oxide, FezlQ, 1.83` Calcium oxide, CaO 1.10 Magnesium oxide,-Mg0 4.10 Potassium oxide', K2O 0.09

Titanium oxide, Ti()2 0.016 Sodium oxide, Na2O 1.04

After treatment with sulfuric acid at the.

Percent. Loss on ignition, H2C 20.6 Silica, Si()2 61.0 Alumina,Al2C3 15.0 Magnesium oxide, Mg() 2.9 1 Calcium oxide., CaO .5

Such clarifying and decolori'zing agents When'vemployed to clarify and improve the color of petroleum oil in accordance with the process described in United States Letters i Patent Nos. 1,404,374 and'1.404,375. granted to Marvin L. Chappell and Merle M. Moore, or employed in any other preferred manner f 60 is connected a pipe 50, provided with suitable Ventura `or tahclays, such vclays having the following analysis In the'process of the present invention, l employ an organic solvent containing va water solution of sulfuric acid of such strength that the sulfuric acid will not react on the organic solvent. The Yorganic solvent to be employed may containeither an alcohol or ketone, or a mixture of alcohols and 'ketones. F or example, acetone, methyl-ethyl ketone, etl1 vl'ketone, or ethyl propyl ketone of a pump' 9. To the inlet' end may be employed, of which acetone, for commercial reasons, is preferred. Also methyl, ethyl, prop vl or butyl alcohol may be employed. To the color solvent is preferably added a solvent suitable to dissolve such mineral oil as may be left inthe clarifyingand decolorizing agent.' Such oil solvent may be a hydrocarbon derived from petroleum oil or Yan organic hydrocarbon such as benzol, tol,- uol. xylol, or mixtures of any such or like mineral oil solvents.

As an example of the organic solvents which are to be elnployed in the process, I

have employed the following admixtures by volume: .(1) gasoline, 60 parts, ethyl alcohol, 30 parts, acetone, 10 parts; (2) or gasoline, 60 parts, acetone, 40 parts 100 parts, or gasoline, 60 parts, cohol, 30 parts, methyl alcohol, 10 parts. The first admixture is generally preferred. To .these admixtures, therefis added at least for .the first step of the treatment, a quantity of relatively weak sulfuric acid, such as about 5001Beaum, for example, 2 volumes of 50" Beaum acid to 100 parts by volume of any one of the above admixtures.

The processof the present invention will be more readily understood from a' description of a specific example of a process embodying the invention and for this purpose, reference is'made to the accompanying'drawings which illustrate diagrammatically an apparatus in Which the process may be carried out. v i

In the drawings, 3 represents a tank provided at'its top with a man hole 2 into which a conveyor 1 is positioned to empty, said conveyorleading from a source fof spent agent (not shown);` To the bottom of the tank 3 valves 32 and 33 which lead to the outlet end of the pump 9 is connected to a pipe- 6, controlled by valves -5 and `7, terminating in tank 3 in the swing vided with 4a pipe 56 which is tion tank 30 and a solvent mixture tank 2T atthe bottom of said tanks. Said tanks are provided With inlet pipes 51 and 54 con' trolled by valves 53 and 52, which lead to a source of said solvent acidsolution and solvent solution mixture not shown).

The bottom of tank 3 is connected by pipe l 55 and controlled by valve'34 which is conf nected to theinlet end of pump 35 and the outlet end ofythe pump is connected to a iilter' 36. The filter 36 may be of any well known type, either operated under vacuum `or pressure and is provided with a pipe 3T lcontrolled by a valve 38 which pipe is arranged to conduct filtered liquid to a used solvent tank 12. Pipe 11, controlled by ,valve 10, connects the outlet end of pump 9 to the top of said tank 12. Tank 12 is proconnccted to the inlet end of pump 14 controlled by a valve 13, the discharge end of the pump connecting through pipe 15, controlled by avvalve 16 with a still 1'?.

The still 17 maybe of any preferred construction, which should preferably be pro- -vided'v with a draw-olf pipe 18, including a pump 21 and valves 19 and 22 on opposite sides of the pump. Vapor pipe 23 leads from the top of the still 17 to a condenser 24` which dischargesthrough a pipe controlled by a `valve 26 into the top of a solvent mixture tank27. The still 40 with 'a mechaniical stirrer 47, is positioned under .the filter '536, with conveyor 39, by means of which the pressed lagent may be introduced into thestill l 40 through a man hole. A suitable steam jacket is provided around the still 40.

Vapor pipe 25 leads from still 40 to con- -denser 24 which discharges into' the solvent mixture tank 27, controlled by valve 26. A man hole is provided at the bottom of still 40 and a conveyor 42 to carry awayc the finished agent. Pipe 54 controlled by valve 52, leads from the top lof the solvent mixture tank 27 to a source of solvent solution (notshown). Pipe 51 ycontrolled by valve 53 leads fromthe top of the acid solution tank 30 to a source of acid mixture (not shown).

n operating the` process, the solvent mixture containing sulfuric acid inv solution contained in tank 30 is introduced into treating tank 3 through pipe 31 through operation of pump 9.

Any ofthe previous examples of a suitable solvent mixture may be employed. The i, solvent containing bothA gasoline and either an alcohol or acetone constitutes both an oil and color solvent. No sulfuric acid should be addedto the admixture contained in tank 27 but to the admxture in tank 3() is added from 1 to 5 volumes of 50" Beauml sulfuric acid or other quantityof sulfuric acid, it

being understood 4that the strength of the.

' and valves 7 and 5 areopened, which permits the acid solvent mixture to circulate under the a'ctlon of pump 9 back and forth into the tank 3, thus producing -an agitation therein.

The desired quantity of spent clarifying and decolorizing agent is then introduced into Atank 8 by operation'of the conveyor 1. The

relative proportions of acid solvent .mixture and clarifying land `decolorizing agent may be wldely varied.. However, in practice, it is found convenient to employ approximately v6 pounds of agent for every gallon of solvent mixture during a single washing operation. i

Y The agitation of the acid solvent mixture 3o is maintained during-the introduction ofv the spent clarifying and decolorizing agent and continued thereafter until the solvent effect of said solvent is completed, after which pump 9 is stopped and the mixture is allowed to stand until the washed decolorizing and clarifying agentlhas settled to the bottomA l solvent mixture may be decanted therefrom' 40l of the treating tank 3. The swing pipe 4 is then adjusted so that most of the used acid and discharged into used solvent tank 12. In a similar manner, the said agent may 4 be repeatedly Washed withy acid solvent mixvture and finally given one or two washes with.

' a solvent mixture lfrom tank 27 which-is free l "40, which isheatedvby steam around' thefrom acid. Thereafter, the washed agent is Vconducted tol filter 36 wherein most of the used solvent mixture is separated from the washed agent by a filter pressing operation.

The washed and pressed agent still containing a lsmall percentage of s olvent mixture passes from filter press 36 into evaporator The solvent mixturemay thus be repeatedly' reused in the process. As soon as the washed and treated agent is free of the solvent mixture, it is conducted to a storage by a conveyor 42 and can be used to again clarify anddecolorize petroleum or other mineral oil.

The used solvent mixture contained in tank l2 ais recovered for reuse by a distillation operation.

' After the distillation operation of the used solvent 1nixture,there remains in the bottom, -of still 17 the petroleum oil which was regained from the agent in the clarifying and decolorizing operation, the coloring matter of which was extracted, and the sulfuric acid employed in the solvent acid mixture. This mixture of oil, coloring matter and acid is delivered to a .storage (not shown) after.

which it may be separated by well known 1 methods.

An important feature of the present invention is the utilization jof an acid solvent mixture containing a relatively small amount of sulfuric acid. The sulfuric acid employed should not bel generally over 5 per cent by volume of the acid solvent solution and the best results havebeen obtained by employing sulfuric acid in the proportion of 2 per cent by volumeof the solvent employed.

.'As. a specific example'of the vresults accomplished by the present invention, it is found that by employing two washes of an acid solvent composed of 10 perv cent acetone vby volume, 30 per cent ethyl alcohol by volume. 60 per cent gasoline by, volume, to which is added 2 per cent by volume of sulfuric acid and thenfollowing such washing treatment by two washes with the solvent in which the sulfuric acid is omitted, the decolorizing agent is reviviied so that it possesses an efficiency of from 105 to 115 per cent of the efficiency of the material before its original use.

The used solvent mixture contained in tank 12 contains a small percentage of sulfuric acid, which may be neutralized by the addition ofthe necessary quantity of pulverized sodium carbonate or other neutralizing agent before the distillation operation for the recovery of the solvent mixture and by this method, there will be avoided the necessity of employving a lead liningin still 17.

While a particular method of revivifying spent clarifying and decolorizing agents has 4been described, it is understood that, various -employed inthe treatment of mineral oil and contain as their basic ingredient, hydrous aluminum silicate in a ratio of less than 1 part of alumina A120,x to 4 parts of silica Sion which comprises washing the spent silicate with a ycolor solvent containing, less than 3% furie acid.

sulfuric acid, and tliereafter washing said" which process comprises washing said spentl silicate with a color solvent free from sul- 2. A process `of-treating spent-clarifying Aand decolorizing agent which has been employed for the treatment of mineral oils and has been prepared bythe acid treatment of` a clay of the Montmorillonite type, which` process comprises contacting the spent agent with a -color solvent containing sulfuric acid, and thereafter Washing said agent with a color solvent free from sulfuric acid.

3.v A process of treating spent clarifying anddecolorizing agents which have been employed in the treatment of mineral oils and which have been derived from the sulfuric acid treatment fof Montmorillonite. clay,

agent with a coln'bined color and o'il solvent containingless than 3 er cent by weight of sulfuric acid, followed y one or'more washes vwith a solvent free yfrom sulfuric acid.

`izing agent which `has been employed on mineral oils and prepared by acid treatmentof a clay of the Montmorillonite type conlprising, Washing the clay with a mixture containing an oil solvent, a color solvent and a l -water solution of sulfuric acid, and thereafter washing the clay with afsolvent free from sulfuric acid.V v 1 y Signed at Washington, D. C., day ofMarch 1926. i MARVIN L.l CHAPPELL.

this 24th 4. A process of activating a spent decolori i 

